Iminoester resins



:hydric alcohol,

Patented Feb. 21, 1950 .IMINOESTER REsINs Warren D. "Niderhauser,PhiladelpfiiwandiflermamArBrusomRsidal, Pa.,1asslgnors,:bymesnerassi-gnmentsr-to-Rohm & HaasrGomnannPhila- 1delphia, ,Pa.,ea mrpcnationof Delaware 1 No Drawing.

This invention 'concerns noveLr-esins ;prepared by reacting togetherthree components, aipolyan .aldehydoemonocarboxylic acid, and'a(ii-primary amine. Inplace of a free monocarboxylic-acid, there may beused an ester thereof form-ed with avolatile alcohol.-

The resins *of this invention are preparedby heating .apolyhydricalcoholwith an laldehydomonocarboxylic acid (or-anesterthereof) toform .apolyester and heating-this polyester with adiprimary amine to form aresinous product.

Forbest results, at least two mols of: aldehydemonocarboxylic acid-arereactedwith one mol of .polyhydric alcohol. This minimum proportionofacid to-alcohol is suificient .to'form at leastaidi- 1 acid ester. Withtri'hydri'c, tetrahyd ri'c, orihexahydric alcohols up to three, four, orsixmolsre- "spectively. of acids may bexreacte'd per mol of a saidalcohol. Excess alcohol, if used, merely=remains in the reaction mixturewhereas,'when 2.1- .cohol is used in anamount insuflicient-to react withall of the acid, thefree acidgroups-mayi be readily reacted with anexcess of amine.

At least one mol of a di-primary amine is used per mol 'of poylhydricalcohol and as many-mole of such amine may'beused asthere are mole ofaldehydo-monocarboxylic .acid in the reaction mixture. Thus, when sixmols of aldehyde-carboxylic acid are taken, six molsof said-amine may beused. While it is'desirable torreact alcohol,

acid, and amine in approximately balanced stoichiometric proportions,satisfactory resins for many applications are nevertheless obtained whenexcess is taken of alcohol or amine. When the proportion of polyhydricalcohol to amine is one to one, the primary condensatesformedareessentially linear in character, and solubility andfusibilityareretained even in'the case of trifunc- "tional or higherfunctional alcohols with or without equivalent proportions ofaldehyde-acid.

' With alcohols of functionality greater than' two -used with more thantwo mols of aldehydo-acid per mol of such alcohol, the-primarycondensates with excess amine are fusible but may become thermoset onfurther heating.

As aldehydo-monocarboXyli-c acids, there may sary that the compound bepurely :aliphatic.

"While it may be such, it may-also be a mi-xe'dtaliphatic compound,including 'aryl aliphati'c and alicyclicaliphatic.

The aliphatic aldehydo-monocarboxylic acids "of "the formula ,onconna-co'on' raridtheir simple esters; wherein :CnHZnQiSI anallgylenagroup, I I straight orbramthed; (of at "least two carbon teway,yet estersthrough'hexyl up to octyl orii- -Application. February 21,1946, Serial No. 6495392 :2 Claims; (chase-e72) ..a.toms in; lengthrand:n is an lntegerhavingia value ofil at least-two, commonly .varyingifromttwoizto sixteemareof particular interest. Typicalcofitheacidssummarized bythe'formula OHC--'(CH2) n COOH.arezomega-ealdehydo-propionic acid, omegaealdehydo-butyric acid,omegaaldehydo-valeric acid, and omega-raldehydoeoctoic acid.

Branched chained -:a;cids 1 or the formula RI 0Ho(. -.oHzoHo.ooH

wherein R is hydrogen .or an alkyl group and R" is an aliphatichydrocarbon group, form another class of importance. The group R." maybe saturated or unsaturated.v Typical of these acids are fi-carboxyethyldiethyl acetaldehyde OHCC(GzH5)-2CH2CH2COOH fl-carboxyethyl ethyl butyl'acetaldehyde O'HCGC'CzI-It) (CH-I9)- CHiCHzCOOH fi-carboxyethyl ethylbutenyl-I acetaldehyde OI-ICC (CzHs) (CH=CHC2H5) CHzCHzCOOH orB-carboxyethyl dimethylacetal'dehyde OHCC(CH3).zCH2CHzCOOI-I andhomologues thereof, including. :those =;described-inUnited StatesPatentNo. 2,342,607.15.- sued February :22, .1944. In the above-namedcompoundsRis an alkyl group of one to two car- .bon atoms rand R" is analiphatic hydrocarbon group of .one .td-four carbon atoms.

Another useful sub-group of .aldehydoecar- .boxylic acids and. theiresters whichmeet the :.requirements of this invention is comprisedof;alicyclicaliphaticicompounds such as are formed by the. addition of.acrolein or crotonaldehyde to ali- ,phaticrcarboxylic acids or estersvhaving axconju- :gate diolefiniclinkage, as in eleostearic orl-icanicracids. Aldehydo monocarboxylic acids and esters oftthisl type aredescribed. in application Serial. No. l623-,442,ifiled. October 1 9,1945 now abandoned. Resins based on acidsof-this,typesare characterized,generally .by beingso'fter. and solubleiin a greater -.variety 1 of...solvents than resins based. .on other types otacids. .The resins from:theaali- 'cyclicaliphati'c" acids are particularly useful asnon-volatile non-migrating softeners for other resinous-materials. I

As" has" been indicated,1'theremaybeusedqesters insfiead dfthe freeacids. Esters-of the lower aliphatic alcohols areparticularlytsuitable-,,a as:these .aicohol. gronpscanreadily-:bereplacedi: by transesterification with a polyhydric alcohol.Esters of, "methyl, ethyl, "propyl, and i-butyl alcohol are particularly"susceptible :to'"replacement 'in.

ethyl hexyl-may be used with the same end effect.

As polyhydric alcohols, there may be used the glycols and aliphaticalcohols of higher functionality, dipentaerythritol, mannitol, glycerol,phenyl glycerol, diethylene glycol, dipropylene glycol, triethyleneglycol, propylene glycol, ethylene glycol, trimethylene glycol, and thelike. There may also be used cycloaliphatic alcohols such as thecyclohexyl diols or triols or inositol.

For this invention, there are mary amines, the amine groups of which areseparated by a chain of at least four atoms as, for example, occurs intetramethylenediamine, pentamethylene'diamine, hexamethylenediamine, anddecamethylenediamine, or isomers, or homologues thereof. Thesedi-primary amines, which form a group of considerable importance, may berepresented by the formula NH2-C1LH2n-NH2, wherein CnHZn is an alkylenechain of at least four carbon atoms and n is an integer of at leastfour, usually varying from four to ten.

Related to these diainines are arylaliphatic anddicyclicaliphatic'diamines such as NH2CeH4 (CI-I2) nNH2 where n is asmall integer,

CoH-C H C HzNHg zCHzCH NH NH; (0 Hz) 3 2) a Hz or 1,4-diaminocyclohexaneand its homologues, or such amines as:

011F013. OHo-Cfi CHr-CH (211mm Aromatic diamines form another importantjsub-class, typical of which are NH2C6H4NH2 and NH2CsH4 CGH4NH2.

In these compounds as in 'all of the amines described or named above itis, of course, necessary that the amine groups be separated by at leastfour carbon atoms. As

shown by the above illustrations, as many as thirteen carbon atoms mayseparate the two amino groups.

amine, triethylenetetramine, N,N-diaminopropyldiaminoethane, and thelike.

The reaction appears to proceed according to the following steps, thesimplest case being shown for purposes of illustration:

OI-ICRCOOR'OOCRCHO onccacooa'oocacn The particular terminal groupswill,-of course,

vary with the proportions and method of re];

including glycerine, pentaerythritol,"

sorbitol, methyl required dipri- In effecting the reaction, it isgenerally preferred to effect esterification of polyhydric alcohol withaldehydo-monocarboxylic acid. This may be accomplished by heatingtogether these components without or with a catalyst, such as zincchloride, sulfuric acid, phosphoric acid, or other acidic catalyst. Thewater of esterification may be driven off with heat or removedazeotropically with a, solvent, such as benzene, toluene, naphthalene,ethylene dichloride, etc. An inert gas, such as hydrogen or nitrogen,may be passed through the reaction mixture to prevent deterioration byoxidation and to help carry away the volatile products formed.

If an ester of the aldehyde-acid is used, the volatile product is thealcohol displaced by the polyhydric alcohol. In some cases, suchtransesterification is desirable, particularly because it permits theuse of an alkaline catalyst, such as sodium methylate, in place of anacidic catalyst. Esterification and removal of volatile products,including any solvent which may have been used at the start, may beeffected at temperatures of C. to over 200 C. and reduced pressure maybe applied to assist in completing the reaction.

A di-primary amine may be added to the ester of polyhydric alcohol andaldehydo-acid and the resulting mixture heated at 150 to 300 C. Again,volatile products are removed. An inert gas may be passed through thereacting mixture and/or vacuum may be applied.

The products vary from viscous syrups and balsams to hard, flexibleresins. They are useful as resinous softeners, tackifiers, orplasticizers for other resins, particularly resins of the nylon type.Some products are useful in coating compositions and hot-melt coatingsor for forming films.

Typical examples of the preparation. of the resins of this inventionfollow.

Example 1 A mixture of 8.44 parts of the product formed by esterifyingone mol of ethylene glycol with two mols ofZ-(p-carboxyethyl)-2-ethylhexen-3- al, and 3.44 parts ofdecamethylenediamine was heated for thirteen hours at 210 C. while aslow stream of nitrogen was passed through the melt. The system wasevacuated and the resin was heated an additional hour at 210 C. at 4 mm.pressure. The resulting resin was a thick amber syrup, readily solublein cold alcohol, benzene, or ethylene dichloride, but insoluble in hotpetroleum ether. Flowouts of the resin from butanol solution containingcobalt drier dried at C. to hard, flexible, tack-free films.

Example 2 Example 3 Amixture of 7.40 parts of the product prepared byesterifying one mol of ethylene glycol with two 75 mols oiZ-(B-carboxyethyl) -2- ethylbutyraldehyde and 3.44 parts ofdecamethylenediamine was gradually warmed to 214 C. over a period offour hours while a slow stream of nitrogen was passed through the melt.The product was heated two more hours at 214 C. under 1 mm. pressure.The resulting resin was a thick red syrup, readily soluble in butanol.

Example 4 A mixture of 9. parts of the product obtained by esterifyingone mol of diethylene glycol with two mols of 2-(fi-carboxyethyl)-2-ethylhexaldehyde and 2.32 parts of hexamethylenediamine was heatedfor one hour at 100 C., for one hour at 210-220 C., and for two andone-half hours at 210-220 C. at the reduced pressure of 3 mm. while aslow stream of nitrogen was passed through the melt. The product was atacky, fusible, orange resin.

Emample 5 A mixture of 9.40 parts of the product obtained by esterfyingone mol of diethylene glycol with two mols ofZ-(B-carboxyethyl)-2-ethylhexaldehyde and 1.03 parts ofdiethylenetriamine was subjected to the same heat treatment given inExample 4. The product was a reddish-brown syrup of much lower viscositythan the resin mentioned in Example 4.

Example 6 A mixture of 10.76 parts of the product prepared byesterifying one mol of decamethylene glycol with two mols of2-(/5'-carboxyethyl)-2- ethylhexaldehyde and 344 parts ofdecamethylenediamine was heated in a slow stream of nitrogen for onehour at 100-l05 C., for 1.3 hours at 190-205 C., and finally for twohours at 205-215 C. under 3 mm. pressure. The product was a tacky,fusible resin.

Example 7 A mixture of 12.96 parts of the product obtained byesterifying one mol of glycerol with three mols ofZ-(p-carboxyethyl)-2-ethylhexaldehyde and 5.16 parts ofdecamethylenediamine was heated in a slow stream of nitrogen for 1.25hours at 100-110 C., for 1.3 hours at 200-215 0., and then for two hoursat 2l0-215 C. under 3 mm. pressure. The product at this stage was atough, fusible, ba1sam-like resin.

Example 8 A mixture of 8.64 parts of the product obtained by esterifyingone mol of pentaerythritol with four mols of Z-(fi-carboxyethyl)-2-ethylhexaldehyde and 3.44. parts of decamethylenediamine was heatedin a slow stream of nitrogen for one hour at 120-160 C., for one-halfhour at 200-210 C., and finally for two hours at 205-215 C. under 4 mm.pressure. The product was a tough, brown, iusible resin.

Example 9 A mixture of 7.34 parts of the product obtained by esterifyingone mol of mannitol with three mols ofZ-(Bwarboxyethyl)-2-ethylhexaldehyde and 2.53 parts ofdecamethylenediamine was heated in a slow stream of nitrogen for onehour at 140-190 C., for one-half hour at 210-215 C., and for two hoursat 212-217 C. at 4 mm. pressure. The product was red fusible resin whichcould be drawn into elastic tack-free fibers.

Example 10 A mixture of 7.34 parts of the product obtained byesterifying one mol of sorbitol with three mols of2-(B-carboxyethyl)-2-ethylhexaldehyde and 2.58 parts of decamethylenediamine was heated for one and one-half hours at -220 C. and then fortwo hours at 211215 C. under 4 mm. pressure. The product was a tough,reddish, balsam-like resin.

Example 11 A mixture of 5.46 parts of the product obtained byesterifying one mol of mannitol with two mols of2-(fi-carboxyethyl)-2-ethylhexaldehyde and 1.72 parts ofdecamethylenediamine was heated in a slow stream of nitrogen for onehour at 100-200 C. and for two hours at 210-215 C. under 3 mm. pressure.The product was a tacky red-brown resin which could be drawn intoelastic fibers.

Example 12 A mixture of 6.73 parts of the product obtained by esterfyingone mol of dipentaerythritol with six mols of 2-(5-carboxyethy1)-2-ethylhexaldehyde and 2.58 parts of decamethylenediamine was heated ina slow stream of nitrogen for 1.3 hours at 95107 C., for one hour at195-215 C., and for two hours at 210-215 C. at 4 mm. pressure. Theproduct was an orange-red fusible resin.

Example 13 A mixture of 6.13 parts of the product obtained by esterfyingone mol of dipentaerythritol with two mols of2-(p-carboxyethyl)-2-ethy1hexaldehyde and 1.72 parts ofdecamethylenediamine was heated for one hour at 200-207 C. and for twoand one-quarter hours at 209-212 C. at 4 mm. pressure. The product was afusible resin.

We claim:

1. The process of preparing resinous materials which comprisescondensing together two molar proportions of glycerol, three molarproportions of decamethylene diamine, and six molar proportions of2-(beta-carboxyethy1) -2-ethylhexaldehyde in successive steps consistingof condensing the glycerol with the Z-(beta-carboxyethyl) -2-ethylhexaldehyde at a temperature between 80 C. and 200 C. and reactingthe resulting condensate with said diamine by heating them together atC. to 300 C.

2. The product obtained by the process of claim 1.

WARREN D. NIEDERHAUSER. HERMAN A. BRUSON.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,197,357 Widmer et a1 Apr. 16,1940 2,310,943 Dorough et a1 Feb. 16, 1943 2,342,607 Bruson et al. Feb.22, 1944 OTHER REFERENCES Ser. No. 382,947, Hans Bergk (A. 1?. 0.),published April 20. 1943.

1. THE PROCESS OF PREPARING RESINOUS MATERIALS WHICH COMPRISESCONDENSING TOGETHER TWO MOLAR PROPORTIONS OF GLYCEROL, THREE MOLARPROPORTIONS OF DECAMETHYLENE DIAMINE, AND SIX MOLAR PROPORTIONS OF2-(BETA-CARBOCXYETHYL)-2-ETHYLHEXALDEHYDE IN SUCCESSIVE STEPS CONSISTINGOF CONDENSING THE GLYCEROL WITH THE2-(BETA-CARBOCXYETHYL)-2ETHYLHEXALDEHYDE AT A TEMPERATURE BETWEEN 80* C.AND 200*C. AND REACTING THE RESULTING CONDENSATE WITH SAID DIAMINE BYHEATING THEM TOGETHER AT 150*C. TO 300*C.